Process for hydrocarbon conversion in presence of added terpenes plus nonmetallic bromine compounds



PatentedMay 1-1, 1948 PROCESS FOR HYDROCARBON CONVERSION IN PRESENCE OF ADDED TERPENES PLUS NONMETALLICBROMINE COMPOUNDS Hillis 0. Folkins, Skokie, Ill., assignor to The Pure Oil Company, Chicago, Ill., a corporation oi No Drawing. Application March 8, 1948, Serial No. 853,125

20 Claims.

This invention relates to a method for conversion of hydrocarbons and more particularly to the conversion of liquid hydrocarbons boiling above the gasoline range to hydrocarbons boiling 7 2 7 approximately 650 to 1200 F., under pressures which may be atmospheric or superatmospheric. As organic bromine compounds for use as sensitizers, I prefer" to use non-metal containing within the gasoline range or to the conversion 5 compounds and more particularly brominated allof hydrocarbons boiling within the gasoline range phatic compounds or cyclic compounds containto hydrocarbons of higher octane value. ing a bromine-substituted aliphatic side-chain. I have discovered that non-halogen-contain- As examples oi bromine compounds which may ing terpenes, particularly cyclic terpenes and debe used are ethylene dibromide, ethyl bromide,-. rivatives thereof, when used together with brolo propylene dlbromide, allyl bromide, acetyl bromine, hydrogen bromide, phosphorus bromides m de. r m -a etl a beta-bromo ethyl et y or organic bromine compounds, particularly broether and benzyl brom B mine compounds minated aliphatic compounds or cyclic compounds which vaporize at cracking t p and containing bromine substituted in an aliphatic pre s e or whi h decompose into ne r chain, which are free or metals and metalloids, l5 bromine compounds which vaporize under cracknot only act as sensitizers to increase the yield in c n n are D n of gasoline-boiling hydrocarbons in the cracking Bromine or bromine compounds may be presof higher boiling hydrocarbon oils, but appreent in the mixture undergoing r i g in ciably improve the octane rating of the resultamounts equiv ent t about 11 to by ing gasoline. weight of bromine, based on the total charge,

Terpenes and their derivatives when used alone but I prefer to use bromine or bromine comare eflective to a somewhat limited extent in impounds in an amount not exceeding 0.1% by proving both yield of gasoline and the octane Weight 01 bromine -equivalent since larger value of the resulting gasoline produced in the amounts of bromine orbrominec mp s cracking of hydrocarbon oils. Bromine and brog5 erally have a deleterious effect on the lead susmine compounds likewise are more effective as ceptibility of theresulting. gasoline. sensitizers than terpenes in improving the yield Terpenes, derivatives thereof, such as esters, of gasoline in the cracking of hydrocarbon oils. ethers, alcohols and the amino, nitro, alkyl, aryl However, bromine and bromine compounds when and aralkyl derivatives in which these groups are used in m unts i xc s of b ut 0,1 7 by 30 substituted for one or more hydrogen atoms in, weight (based on bromine equivalent) of the oil the terpene molecule, may be used together with undergoing cracking, have been found to delebromine or bromine compounds. Substances rich teriously affect the lead susceptibilityof the rein ternenes o t e r de v ve ch s turpe suiting gasoline, tine and citronellaoil may be used in place of One of the objects of this invention is to prop r t p nes nd their derivatives. vide an improved method for converting hydro- E amples of terp nes. derivatives thereof, and carbons boiling above the gasoline boiling range substances containing the aforesaid which may. to hydrocarbons boiling within the gasoline boilbe used are as follows: alpha pinene, dipentene, ing range, alpha terpinene, delta carene, sabinene, cam- Anotherobiect of the invention is to provide Phon n my turpentine and citro- 'an improved method for increasing the octane nella oil. The terp nes, their derivatives and value of gasoline boiling hydrocarbons formed substances containing the same, may be used in in the cracking of hydrocarbon oils. concentrations ranging from approximately .01

Still another object of the invention is to into 3% by weight f the h rge. crease the yield of gasoline boiling hydrocarbons Although cracking may be carried out at atfrom higher boiling hydrocarbons and to immospher c Dr SS -lr JDrefer to crack under superprove the octane value of the resulting gasoline. atmospheric pressures upward of 300 pounds per Other objects of the invention will become square inch, since higher yields of desired prodmanifest from the folowing description. ucts are obtained under high super-atmospheric In accordance with my invention, hydrocarbon pressureoil is mixed with a small amount or a terpene The sensitizers may be mixed with the hydroor derivative thereotand with a small amount carbons to be charged to the process prior to of bromine, hydrogen bromide. a phosphorus the entrance thereof into the reaction zone or bromide or organic bromine compound and subthe sensitizers may be flash-injected directly Jected to cracking temperatures which may be ill into the reaction bone after heating suflicientiy to either melt a normaly solid substance or to vaporize a normally liquid or solid'substance.

data and results of these runs conducted at atmospheric pressure.

Table I 1.1010 1.1 010 1.1010 Gaseous below 400 1 13 43 o 21011., Charge. 0 00 m Tam uotl Products F. percent F. per cent duced,Wt. p c 1 Baum! GnLper' Gm. per o'icharge o'icharge Per Cent 1: 82:

Hr. Br. 0! Charge Vol Wt. Vol. Wt.

011 104.0 None 100.2 0.0 12.2 10.0 03.3 03.1 0.0 011 new Turpentine 1 bywtg- 100.0 0.0 14.0 13.1 00.1 00.3 0.0 011 104.0 Turpentine 001110.. 104.4 10.3 14.4 13.0 10.0 00.1 0.3 1.001 011 104.0 Bromine 0.1 bywt.)-. 102.0 14.2 14.0 13.1 10.2 10.4 0.0 1.331 010 104.0 1 3.20 e byg ti). 140.4 10.2 10.0 14.0 10.1 10.0 0.0 1.114 011 104.4 mum-(1 g 103.2 12.1 10.1 13.1 13.0 10.0 1.3 1.120

Bromine (0.20 ,bywt 011 104.0 '1 111100 1.0% b 141.0 10.0 10.0 11.1 123 12.2 10.1 1.100

010113100 (0.17 by 111.). 011 104.0 1111110 (0.0% by 102.4 12.3 10.1 13.1 10.0 10.4 1.0 1.130 001 100.0 g gwjgytg 100.0 10.0 10.1 14.1 10.0 10.2 0.1 1.100

Bromine (0.17 by Wt. 010.2 104.0 this (1.0% by 140.0 13.1 10.1 14.0 10.4 11.0 0.4 1.120

Where flash-injection is practiced, care should be exercised not to heat the sensitizers above their decomposition temperature prior to injection into the reaction zone.

In order to demonstrate the eflectiveness of the combination sensitizer, a series of runs was made in a continuous laboratory apparatus using Pennsylvania gas oil as charging stock. The gas oil had the following characteristics:

From an examination 0! the data in Table I it will be seen that both bromine and turpentine when used alone increase the yield of liquid hydrocarbons boiling up to 400 F. The results further show that there is no advantage in usin 2% oi turpentine instead oi 1% insofar as yield is concerned. The results in general show that the combination of bromine and turpentine gives a higher yield of lower boiling hydrocarbons than Percent byweight boning up to F" m 35 does either the bromine or turpentine alone. Gravity 1 9,9,3 The results of the runs conducted under sugr 0,8360 peratmospheric pressure are recorded in Table Wt. lbs. per gal 6.878 I1. Table II Octane No. of 100-400 00110101101 Yield in Wt. per cent of Charge F. containing TEL Press. Charge gg Goaltemmwm Run Lbs. Temp., retain cove, oov NO. P g F. 4 Gal Ou- 0 04 .111. in-n1. wt. m pei'Hr. and 100- 400- o.0 0.0 1.0 2.0 3.0 Name per C; we 400 000 R00. Loss 00. cc. co. co. co.

cent r. F.

11---- 000 001 1.012 None..-; .004 2.213 22 0.0 3.3 14.1 00.3 0.0 1.0000020000001112 12.... 000 000 1.001 3101111110..-. 000 0.000 2.310 2.1 0.1 3.2 20.1 00 11.0 0.0004041010100104 13.-.. 000 001 1.000.....00 0.01 0.010 2.122 20 0.0 3.0 11.0 04.1 22.1 01 01.4011 011.000.011 14- 000 001 1.000 Turpentine- 1 0.000 2.430 2.4 0.1 0.0 10.0 10.0 3.0 0.0 00.001011000011111 10.... 000 001 .00 .410...-" 2 0.001 2.400 2.3 0.0 02 100 10.0 0.0 0.1 00.002110031121011 10.... 000 001 1.000 325 #32 0.003 2.408 2.0 0.1 3.0 10.0 01.1 0.4 0.1 00.0 02.0 00.0 11.3 143 11-... 000 001 1.000 way .95 0.001 2.180 2.4 0.0 2.2 10.0 02.0 12.2 0.1 010.000.0001 12014.1 10..-- 000 000 0000 megafigs 0.010 1.400 2.3 0.1 3.3 20.1 04.4 10.0 0.0020013104130103 000 001 1002 03 3;: i8}, 0.003 2.324 2.2 0.0 10.1 040 20.0 0.0000020010112100 20.... 000 887 0.000 $2"; $3 0.088 2.000 2.2 0.0 3.2 10.0 04.0 0.0 0.2013012102100100 Pour, F 3 From an examination of the data recorded in Unsaturates, wt. per cent.........- Lessthan 3 Table 11, it will be seen that from a yield stand- Bromine N 2.3 point, there is no advantage in using turpentine Molecular weight 250 in conjunction with bromine, since bromine A series of runs was carried out at atmospheric pressure and at a temperature 01 approximately 525 C. (977' F). Another series of runs was carried out at a pressure of 500 pounds per square inch and at approximately 475 0. (877 F. In order to form a basis'oi comparison. runs were made in which (1) no sensitizer was used; (2) turpentine alone was used: (3) bromine alone was used; and (4) both bromine and turpentine were used. Table I gives the tabulated "line.

alone under the conditions or the reaction gave at least as good a yield as the combination sensitizer. However, an unusual result was obtained with respect to octane number appreciation. This can be readily seen by comparison of the data for runs 11, 13, 14 and 19. Bromine in the amount of .01% when used alone and turpentine in the amount of 1% when used alone have very little eflect on the octane rating or the gaso- However, the combination of the two inber over that obtained with- 2%, and increase in the amount oi. bromine above 0.1% delete riously aflects the lead susceptibility of the gasoline. Thus, by using the combination of a very small amount of bromine with turpentine, not only are the yields of gasoline over those obtained without sensitizer considerably improved. but the octane rating and lead susceptibility are higher than can be obtained by using either bromine or turpentine alone. v

Another seriesof runs was made to demonstrate the effect oi the combination of phosphorus tribromide and turpentine as a sensitizer in the cracking oi mineral oils. Pennsylvania gas'oil was cracked in .the same laboratory apparatus used for making the runs recorded in Tables I and II, at temperatures of 525 C. and atmospheric pressure. The data for the various runs is recorded in Table III. 1

or the fluid type. when applying my invention to known types of cracking operations, it is merely necessary to provide'i'eeding and proportioning means for ieeding sensitizer to the hydrocarbons undergoing cracking.

It is claimed:

1. The method of cracking hydrocarbon liquids to gasoline boiling range hydrocarbons comprising subjecting said liquids to cracking conditions of time. temperature and pressure in the presence oi" a small amount of a substance, effective to sensitize the reaction materially, selected from the group (1) consisting of bromine, hydrogen bromide, phosphorus bromides and metaland metalloid-iree organic bromine compounds, and

' a small amount of a. substance selected from the taining material.

group (2) consisting oi halogen-free terpenes and their derivatives.

' 2. Method in accordance with claim 1 in whichthe substance from group (1) is bromine.

3. Method in accordance with claim 1 in which the substance from group (2) is a terpene.

4. Method in accordance with claim 1 in which the substance from group (1) is bromine and the substance from group (2) is a terpene.

5. Method in accordance with claim 1 in which the substance from group (2) is a terpene-con- 6. Method in accordance with claim 1 in which 80 the substancei'rom group (2) is a pinene-con- Table III Ll nid Li uid e Li uid Gase Mi -135 1 a 431 1- 0 a o P arge ous ow a ove c e Run grams Sensitizer and Pro ucts, Products percent percent No. 3! du e d, $2. 3 g No. Per per cent by weight Grams Grams, of charge of charge Gasoline Per cent g Hour Per Hour Per Hour Fraction of Charge of as '01 Wt. v01. Wt.

379.2 31.3 12.0 10. 9 81.1 81. 5 63. 8 7. 6 1.1 341. 3 45. 3 15. 6 14. 2 73. B 74.1 M. 2 11. 7 1. 842. 9 66. 4 21. 9 20. 8 62. 8 63. 5 60. 8 1B. 2 1. 403 380.0 30.8 12.9 11.8 80.3 80.7 64.2 7.5 1. 149 383. 8 27. B 12. 8 11. 6 81.3 81. 7 65. 5 r 6. 7 1. 18 356.,4 51. 2 17. 2 15. 7 71. 1 71. 8 66. 7 12. 5 1. 278 360. 0 48- 6 17. 1 15. 7 71. 9 v 72. 4 66. 3 11. 9 1. 272 2a 40s. a -g ass. 6 as. a 24.1 22. a as. s so. a 05.0 1'7.o 1. are

From an inspection of Table III it is apparent that phosphorus tribromide alone considerably enhances the yield of gasoline per pass obtained, but when used in amount of 0.1% has practically no effect on the octane number oi the gasoline and in amounts of 0.5% has-a deleterious eflect on the octane number oi the gasoline. Turpentine when used alone has only a very slight effect in increasing yield of gasoline, but is more eil'ec- -ing of hydrocarbon oils by increasing the yield of gasoline and by increasing the octane rating and improving lead susceptibility.

My invention is applicable to conventional thermal cracking operations in which no catalyst is used and also to solid catalyst cracking operations oi the stationary and moving bed type brominated aliphatic chain.

the total charge and the group (2) substance is present in amount equal to approximately .01 to 3% by weight or the total charge.

11. Method in accordance with claim 1 inwhich the bromine equivalent of the group (1) substance is between 0.005 and 0.1% by weight of the total charge and the group. (2) substance is present in amounts equal to approximately .01 to 3% of the total charge.

12. The method oi cracking hydrocarbon oils to liquid hydrocarbons boiling within the gasoline boiling range comprising subjecting said hydrocarbons to temperatures of the order of 850 to 1200' .1". in the presence oi a small amount at bromine and a small amount 01 turpentine tor a period of time suflicient to eiiect substantial cracking of said oil, the amount of bromine and turpentine being suiilcient to ei'iect a material sensitization of the reaction.

13. The method in accordance with claim 12 in which the bromine is present in amounts be.- tween 0.005 and 0.1% by weight ,0! the charge.

14. The method 01 cracking hydrocarbon oils to liquid hydrocarbonsboiling within the gasoline boiling range comprising, subjecting said hydrocarbons to temperatures of the order 01 050' to 1200' F. in the presence of 0.005 to 0.1 per cent by weight oi bromine, and 0.01 to 3 per cent by weight of turpentine.

i5. The-method of cracking hydrocarbon oils to liquid hydrocarbons .boiling within the gasoline boiling range comprising, subjecting said hydrocarbons to a temperature of about 887 E, and a pressure of about 500 pounds per square inch in the presence oi about 0.01 to 0.05 per cent by weight of bromine and about 0.5 to 2 per cent by weight of turpentine.

16. Method in accordance with claim 1 in which the substance from group (1) is'a phosphorus bromide.

1'7. Method in accordance with claim 1 in which the substance from group (1) is phosphorus tribromide and the substance ircm group (2) is turpentine.

assaseo 18. The method in accordance with claim 1 in which the substance from group (1) is ethylene 4 dibromide.

19. The method in accordance with claim 1 in which the substance irom group (1) is ethylene dibrornide and the substance from group (2) is turpentine.

20. The method of cracking hydrocarbon oil comprising subjecting said oil to suitable cracking conditions of time. temperature and pressure in the presence of phosphorus tribromide in an amount not in'excess of approximately 0.1% by weight and turpentine in an amount not in excess of approximately 1% by weight.

311.115 0. FOLKINS.

REFERENCES CITED 1 The following references are 0! record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,295,752 Parkhurst Sept. 15, 1942 2,305,635 Rice et a1 Dec. 22, 1942 2,388,428 Mavity Nov. 6, 1945 FOREIGN PATENTS Number Country Date 11,397 Great Britain, 1912 Feb. 13, 19 

